CS219666B1 - Mixed difunctional catalyst for catalytic hydroconversion of hydrocarbons and processes for its production - Google Patents

Abstract

The invention relates to a catalyst suitable for catalytic hydroconversion of hydrocarbons and a method of its production. The catalyst comprises two aluminosilicate components and a metal component. One aluminosilicate component is a synthetic aluminosilicate containing bound metals, the second component is selected from the group comprising aluminosilicates of various types and origins. The metal component is selected from metals of groups 6 to 8 of the periodic table. The method of production of the catalyst comprises homogenization of the individual components and heat treatment under specified conditions. The catalyst can be used in catalytic hydroconversions of hydrocarbons or mixtures of hydrocarbons such as hydrocracking, disproportionation, hydroisomerization, hydrodearomatization, dealkylation, transalkylation and the like.

Description

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BACKGROUND OF THE INVENTION The present invention relates to a novel type of mixed difunctional catalysts effective for the catalytic hydrocarbon conversion of hydrocarbons or mixtures of hydrocarbon processes to produce them.

Hydroconversion refers to the conversion of hydrocarbons or mixtures of hydrocarbons occurring in the presence of hydrogen or hydrogen-containing gas. Hydroconversion of hydrocarbons contemplated by the invention relates to hydrocracking, disproportionation, hydrodearomatization, hydroisomerization, disalkylation, catalytic reforming, transalkylation, and similar processes of overfunctional catalysts.

More specifically, under the catalytic hydrocarbon conversion of hydrocarbons or mixtures of hydrocarbons, the hydrogenation cracking of petroleum distillates or hydrocarbon distillates obtained from coal processing is understood; hydroisomerizing alkanes, cycloalkanes, alkylated aromatic hydrocarbons, alkenes and / or mixtures thereof; hydrogenation dearomatization of motor and jet fuels; disproportionation of alkenes, cycloalkenes and alkyl-substituted aromatic hydrocarbons; disalkylation of alkylaromatic hydrocarbyl transalkylation of aromatic hydrocarbon mixtures with various alkyl substituents catalytic reforming of hydrocarbon distillates boiling in the gasoline distillation range * Considered hydrocarbons or mixtures of hydrocarbon moieties, but do not need to include sulfur and / or nitrogen compounds as accompanying substances. In many chemical processes, natural or synthetic aluminosilicates which are either amorphous or crystalline are used as catalysts. These aluminosilicates together with metals 6-8. periodic groups (e.g., Mo, Re, Pt, Pd, Ni, Co, Ir, etc.) in the form of difunctional catalysts are used in large scale in hydroprocessing such as hydrocracking, hydroisomerization, disproportionation, transalkylation, and the like.

Thus, the difunctional catalysts contain two active components; aluminosilicate (acidic component) and metal, respectively. its compound (hydrogenation / dehydrogenation component). Difunctional catalysts contain, as the acidic component, a crystalline zeolite, which in most cases is more active and selective than amorphous aluminosilicate-containing catalysts. More potent difunctional catalysts include those containing the H-formusynthetic mordenite.

The present invention relates to a novel type of difunctional catalysts which are more active and more selective and have differentiated catalysts containing as the acidic component the H-form of the synthetic mordenite. The described difunctional catalysts according to the invention can be called mixed di-catalysts in view of the phase composition of the acid component of these catalysts.

Mixed difunctional catalysts according to the invention suitable for the catalytic hydroconversion of hydrocarbons or hydrocarbon mixtures are prepared by mixing together the individual aluminosilicate-219666 components A and B, where component A is understood to be a synthetic layered aluminosilicate having a chemical formula

m SiO2: n A12O3: p QO: with DM: t H2O in which it denotes

SiO2 silicon dioxide A12O3 alumina QO metal oxide or oxides selected from the group consisting of honey, beryllium, magnesium, zinc, nickel, cobalt, D anions selected from the group consisting of hydroxyl anion, fluoride anion, chloride anion, oxygen anion, M equivalent of exchangeable cation or ka thiones selected from the group consisting of hydrogen, ammonium, alkali metal, alkaline earth metal, HO water, wherein in molar ratios it is from 2.01 to 3.97 n having a value of 0.02 to 2.96 p having a value of 0 , 03 to 3.50 s has a value from 0.03 to 1.00 t has a value from 3.50 to 5.10 at 60% relative humidity,

Component B within the meaning of the invention is understood to be a material selected from the group consisting of alumina, silica gel and / or crystalline aluminosilicates such as type X zeolites, Y type zeolites, halloyzite, natural or synthetic montmorillonite, kaolinite, natural mordehite , a natural butbosynthetic clinoptilolite, mixtures thereof, natural or non-natural or their natural mixed structures. The preparation of the catalysts according to the invention involves the homogenization of the mixture of said components A and B by a dry process (e.g. in a ball mill) and / or by wetting, shaping the homogenized mixture to obtain a catalyst in the form of desired sizes and shapes such as grains, exrudates , tablets and the like. The catalysts prepared according to the invention are further dried at 80 ° C-150 ° C and calcined at a temperature of 150 ° C-700 ° C. In order to obtain difunctional catalysts, it is necessary, prior to mixing the aluminosilicate components A and B, to introduce into these components hydrogenation metals 6 to 8 of the periodic group, such as platinum, palladium, nickel, cobalt, iridium, rhenium, molybdenum and the like. . and / or mixtures thereof with known procedures such as impregnation or ion exchange. The hydrogenation metals can be introduced after mixing the components A and B, i.e. into the mixture of components A and B. By the two processes or by combining them, catalysts having high activity and selectivity are prepared.

The final step in the preparation of the catalysts according to the invention is the reduction of the calcined catalyst in a stream of hydrogen or hydrogen-containing gas in order to convert the metals of the periodic group into an atomic state which is introduced directly into the reactor.

The mixed difunctional catalysts of the invention contain the aluminosilicate components A and B, the content of component A in the catalyst mixture of components A and B being from 10% to 95% by weight. and a metal or mixture of metals of the 7th and 8th periodic groups in an amount of from 0.01% to 6.5% by weight. and in the case of the presence of metals of the 6th periodic group from 0.5 to 25% by weight. weight of the catalyst. Subsequently, the examples illustrate the method of preparation, the advantages and the practical use of the catalyst according to the invention, without, however, limiting the subject matter of the invention in any way. Example 1.

The synthetic Y-zeolite with SiO2: ALO, = 5.1 in ammonium form was mixed with zinc-containing component A and wet homogenized for 8 hours. Then, a solution of [Pd (NH 3) 4] Cl 2 was added to this mixture so that the resulting material contained 0.8% by weight after drying at 110 ° C. palladium, 60% Y-zeolite and 39.2% component A. The dried catalyst, which is designated A, was further calcined at 450 ° C and the reactor coating activated in a stream of H 2 at 420 ° C. Example 2.

Natural clinoptilotite was activated in 0.2 N HCl solution for 3 hours. After subsequent ion exchanges in the ammonium salt solution, a clinic in ammonium form was prepared which was calcined at 450 ° C. A homogeneous mixture was prepared from clinically modified nickel-beryllium-bound component A, and a homogeneous mixture was prepared which was impregnated with H2PtCl6 solution. The resulting B-labeled catalyst contained at 120 ° C; 39.5% clinoptilolite, 30% component A, 30% g-alumina and 0.5% platinum. Example 3. 100 g of natural halloyite, in which the alkali metal ionic ammonium acetate solution was alkali metal removed, was humidified with 11.0 g of component A with structurally bound nickel for 5 hours. To obtain the homogeneous mixture, a solution of [Pd (NH 3) 4] C 12 ”was added such that the obtained catalyst C, after drying at 120 ° C and calcination at 450 ° C, contained 0.48% by weight. palladium. -, Example 4.;

The natural mordenite was treated with acid activation followed by an ionic NH 4 NO 3 solution. The obtained ammonium form was wet-homogenized with component A containing nickel for 6 hours, after which a solution of H2PtCl6 was added to the prepared homogeneous mixture so that the platinum content of the dried catalyst D was 0.6% by weight. 219666

The dried catalyst was calcined at 540 ° C for 2 hours and then activated in a reactor at 480 ° C with hydrogen flow. Example 5.

The catalytic activity of the difunctional catalysts of the invention in the hydrotreating process was monitored on a flow-through microarray-type at a pressure of 0.25 MPa on a hydrocracking model reaction of n-hexane. A synthetic mordenite in H-foe with a molar ratio of 17.6 SiO2 / Al2O3 containing 0.8% by weight was used as a comparison catalyst. platinum. The spatial volume velocity of the injected n-hexane was 1.0h -1.

The reaction products were analyzed by gas chromatography. As shown in the experimental results (Table 1), the catalysts according to the invention are characterized by high activity, the conversion of n-hexane by the catalysts of the invention is achieved at a lower temperature than the Pt / H-mordenite catalyst. Example 6.

The catalytic activity of the catalysts according to the invention in the n-hexane hydroisomerization process is investigated. in an atmosphere of hydrogen at a pressure of 0.25 MPa, a bulk velocity of raw material of 1.0 h “1a at a temperature range of 200–330 ° C. The Pt / H-mordenite industrial isomerization catalyst (0.4 wt% platinum) served as a comparative catalyst. The iso- merisate was analyzed by gas chromatography method. As shown experimentally by the results (Table 2), the catalysts of the invention are distinguished by high activity and selectivity, mainly based on the production of dimethylbutanes, which due to their high octane number are the most valuable hydrocarbons in the isomerism. The selective hydroisomerization activity and the selectivity of the catalysts of the invention is best reflected by the parameter selective conversion to dime; tylbutanes, which is 2.9 times higher than on the current industrial isomerization catalyst, and also the selective conversion parameter to iso-C5 / C6, which is 2.3 times shorter in the catalysts of the invention than in the comparative industrial catalyst (see Tabufka). 2).

Table 1.

Catalyst According to the Invention Comparative Pt / H-mordenite Catalyst A Catalyst B Temperature ° C Conversion of n-hexane (wt%) 220 23.88 21.63 1 14.95 240 41.25 34.84 29.67 260 58.29 57.68 45.91 280. 69.76 76.51 63.77 300 83.69 85.89 79.27 320 91.75 89.71 86.71

Claims (2)

5 Table 2. Catalyst According to the Invention Comparison of industrial Pt / H-mordenite catalysis. C catalysis. D Temperature ° C 260 260 300 Product composition% wt-pentane 8.31 0.45 5.65 n-pentane 6.13 0.37 1.42 2.2-dimethylbutane 9.40 7.26 3.73 2,3-dimethylbutane 4.04 6.72 4.74 2-methylpentane 25.83 34.97 21.02 3-methylpentane 15.76 23.16 13.45 n-hexane 15.98 20.20 20.73 methylcyclopentane 0.56 1.35 0.62 benzene - - 0.07 cyclohexane 0.15 0.34 0.14 dimethylbutanes (DMB) selective. conversion to 13.44 13.98 8.47 DMB selective. conversion to 45.07 55.08 17.24 IZOCg / Cfi 2) 1.78 2.88 0.98 Yield C5 + 86.16 94.82 71.59 0 Selective conversion to DMB - __% DMB__% (C1-4) C2 4- C3 + C4 + nC1) 2) Selective conversion to isoC5 / C6 = _ (% C5-4C6-4cycloC6)% (C (4 * C-2 4 "C3-4C4 * nC5 4") nCg) SUBJECT OF THE INVENTION A mixed difunctional catalyst for catalytic hydroconversion of hydrocarbons or mixtures of hydrocarbons such as hydrogenation cracking, hydroisomerization, dealkylation, hydrodearomatization, catalytic reforming, transalkylation, dispersion, characterized in that it contains aluminum-silicate components A, B and metal component, wherein component A is a synthetic layered aluminate-silicate with the formula empirical formula m SiO 2: n A 2 O 3: p QO: with DM: t H 2 O in which SiO 2 is silicon dioxide * A12O3 alumina QO metal oxide or oxides selected from copper, beryllium magnesium, zinc, nickel, cobalt, 219666 D equivalent of anions selected from the group consisting of hydroxyl anion, fluoride anion, chloride anion, oxygen anion, M equivalent of exchangeable cation or cations selected from hydrogen, ammonium, alkali, alkaline earth, óny Water, with molar ratios having a value from 2.01 to 3.97 n having a value from 0.02 to 2.96 p having a value from 0.03 to 3.50 s having a value from 0.03 to 1.00 t having a value from 3.50 to 5.10 at 60% relative humidity, component B comprises substances from the group such as alumina, silica gel, crystalline aluminosilicates, zeolites X, zeolites Y, halloyzite, natural montmorillonite, synthetic montmorillonite, kaolinite, natural mordenite, clinoptilolite wherein the content of component A in the catalyst is from 10% to 95% by weight, the content of component B being from 5% to 90% by weight. and the metallic particulate in the atomic state or in the form of its oxide or sulphide is selected from the groups 6-8 of the preferred group including platinum, palladium, nickel, cobalt, iridium, rhenium, molybdenum, the metal component of the catalyst being metal 7 and 8. a periodic group of from 0.01% to 6.5% by weight. and in the case of the 6th periodic group, from 0.5 to 25% by weight. 2. A method for producing a mixed difunctional catalytic hydrocarbon conversion catalyst according to claim 1, characterized in that it comprises homogenizing the aluminosilicate constituents A and B in the dry or wet form, further forming the homogenized mixture of components A and B in the particle, drying the particles. at a temperature of from 70 ° C to 150 ° C, calcination of the dried particles at a temperature of from 150 ° C to 700 ° C, preferably from 350 ° C to 550 ° C, and heat treatment in the presence of hydrogen or hydrogen-containing gas at a temperature of; 200 ° C to 650 ° C, preferably from 320 ° C to 480 ° C, wherein the metal component is introduced into the individual aluminosilicate builders A and B prior to mixing or into the mixture of components A and B during or after homogenization, but prior to thermal treatment in the presence of hydrogen or hydrogen-containing hydrogen.